Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
  • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
  • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/355—Temporary coating
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils

Definitions

• the present invention relates to a coated glass article, in particular an article comprising a glass sheet coated with an enamel-based coating.
• the glass article of the invention is heatable, i.e., it can be heat treated with a view in particular to its subsequent quenching.
• the international application WO2007 / 135192 A1 discloses a glass sheet coated with a layer based on of enamel whose mechanical strength before quenching has been improved.
• This type of product makes it possible to avoid claws and damage to the layer itself.
• this type of product undergoes an aesthetic degradation during the manufacturing process and especially its machining: the coated surface of the enamel-based layer has indeed on its surface traces, often dark or even black, left by belts (usually dirty) of transport equipment in factories, such as rubber bands on cutting tables or conveyor belts for automatic rakes. Treatments such as hand washing or even the industrial washing machine are very often insufficient.
• these traces unfortunately remain after the heat treatment for quenching ( ⁇ 670 ° C).
• the enamel-based layer is most often opaque, these traces are not visible when viewed through the glass sheet of the uncoated side and they are not unpleasant in case of single-sided application of the glass product (eg a wall covering).
• the aesthetic degradation nevertheless exists in the case of a two-sided application of the glass product, such as, for example, a partition or a balustrade, and this type of product is therefore unsuitable for sale for this type of application.
• this degradation is even more important that the color given by the enamel-based layer is clear.
• the object of the invention is notably to overcome these disadvantages by solving the technical problem, namely to obtain a glass sheet bearing an enamel-based coating capable of undergoing a heat treatment, in particular with a view to its subsequent quenching, and resistant to transport and handling.
• an object of the invention in at least one of its embodiments, is to provide a glass sheet with an enamel-based coating which, after having been quenched, can be used for two-sided applications. .
• an object of the invention in at least one of its embodiments, is to provide a glass sheet with an enamel-based coating which, after having been quenched, has no or more traces. from transfer tools (eg conveyor belts), processing (eg rippers) and / or handling.
• transfer tools eg conveyor belts
• processing eg rippers
• Another object of the invention is to provide a solution to the disadvantages of the prior art that is simple, fast and economical.
• the invention relates to an article comprising
• the invention is based on a completely new and inventive approach because it solves the disadvantages of glass products of the prior art and solve the technical problem.
• the inventors have indeed demonstrated that it was possible to obtain, by combining an enamel-based coating and a wax, an enamelled glass article (i) which is capable of undergoing a heat treatment, in particular in view of his temper (ii) sufficient mechanical strength before quenching; and (iii) after being quenched, no trace (from transfer, processing and / or handling tools) present prior to heat treatment.
• the inventors have thus demonstrated that the presence of wax in and / or on the enamel-based coating allows the subsequent removal (during a heat treatment) of such traces. This result is surprising insofar as the use of wax in a paint in general is known but to improve the non-stick or slip properties of its surface and not as a trace-removing agent on a coating via a treatment thermal.
• FIG. 1 represents a photograph of an enamelled article according to the state of the art
• Figure 2 shows photographs of an enamelled article according to one embodiment of the invention
• Figure 3 shows photographs of an enamelled article according to another embodiment of the invention.
• the article according to the invention is formed of a glass sheet.
• the glass according to the invention can belong to various categories. Glass can thus be a soda-lime type glass, a boron glass, a lead glass, a glass comprising one or more additives homogeneously distributed in its mass, such as, for example, at least one inorganic dye, an oxidizing compound , a viscosity regulating agent and / or a melt facilitating agent.
• the glass of the invention is of the soda-lime type.
• the glass of the invention may be a float glass, a drawn glass or a printed glass. It can be clear, extra-clear, colored in the mass, sanded and / or matted.
• sida-lime glass is used here in its broad sense and refers to any glass that contains the following basic components (expressed as percentages by total weight of glass):
• the glass sheet is a float glass sheet.
• the glass sheet is a soda-lime float glass sheet.
• the float glass sheet of the invention may have a thickness ranging, for example, from 2 to 10 mm.
• the article of the invention comprises an enamel-based coating on at least one of the surfaces of the glass sheet.
• the coating may extend continuously over substantially the entire surface of the glass sheet, for example over more than 90% of the surface, preferably over more than 95% of the surface. Alternatively, the coating may partially cover the surface of the glass sheet.
• the coating has a decorative function.
• the coating is opaque.
• the coating is colored (including white and black).
• the enamel-based coating comprises a powder consisting of a vitreous matrix (or glass frit) and inorganic pigments, suspended in a medium (or medium).
• the medium according to the invention is preferably of organic nature and preferably comprises thermally crosslinkable and / or photocrosslinkable elements (under infrared or ultraviolet radiation).
• the invention covers (i) the enamel-based coating after drying, i.e. after removal of the solvent (s) possibly present in the initial composition and (ii) if the enamel-based coating is used after crosslinking.
• the enamel-based coating comprises 11 to 40% by weight of organic materials.
• the enamel-based coating does not comprise more than 30% by weight of organic materials and, even more preferably, not more than 20% by weight.
• the coating generally about 1 to 2 grams was removed from the surface of the article after being dried (solvent free residuals) and / or crosslinked and analyzed by thermogravimetry (ATG). The analysis is carried out in air, from 20 ° C. to 1000 ° C., with a temperature increase of 10 ° C./min.
• the organic matter content is determined based on the residue once no further weight loss is observed. Generally, the organic matter is completely burned around 400-500 ° C.
• Such an organic content in the enamel-based coating of the invention makes it possible to obtain a very appreciable mechanical strength of said coating before it is quenched.
• the organic material in the enamel-based coating of the invention may comprise at least one compound selected from the following compounds: polyols, alkyds, acrylics, polyacrylics, polyacrylates, polymethacrylates, acrylamides, melamine, polycarbonates, styrenes, vinyl-acrylics , urethanes, polyurethanes, polyesters, polyolefins, urethane alkyds, polyureas, amino resins, polyamides, epoxides, epoxy esters, phenolic resins, silicone resins, PVC, PVB, aqueous resins and reaction products of the aforementioned compounds.
• the enamel-based coating is in direct contact with the glass sheet.
• an adhesion promoter may be present between the glass sheet and said coating.
• the adhesion promoter may, for example, comprise a silane.
• the enamel-based coating once dried and / or cross-linked, has a thickness of between 20 and 100 microns.
• layer thickness is meant here the average geometrical thickness. If the thickness of the coating is too low, this may result in obtaining an enamelled glass article not having the strength properties mechanical or desired aestheticism; if it is too high, drying and / or crosslinking may not be complete and detachment / degradation of the coating may occur. Such thicknesses can be obtained during the manufacturing process, by one or more application (s).
• the glass article of the invention comprises at least one wax.
• wax denotes an oligomer derived from natural or synthetic polymers.
• the wax according to the invention is chosen from waxes of natural origin, waxes of synthetic origin and mixtures thereof in any proportions.
• the wax may belong to the category of animal, vegetable or mineral waxes.
• Mineral waxes derived from petroleum are preferred and more particularly paraffins and microcrystalline waxes.
• Paraffin waxes consist mainly of linear hydrocarbon chains. They mainly comprise normal paraffin (80 to 90%), and to a lesser extent, branched paraffins and cycloparaffins.
• the wax When the wax is of synthetic origin, it may belong to hydrocarbon compounds obtained by reforming, to halogenated naphthalenic compounds and to ethylene and vinyl polymers.
• the wax is chosen from ethylene and vinyl polymers and polyolefins. Examples of synthetic waxes well adapted to the invention are polypropylene, polytetrafluoroethylene (PTFE), polyvinyl alcohol and mixtures thereof.
• the glass article of the invention comprises at least one wax that is present in the enamel-based coating.
• the glass article of the invention comprises at least one wax that is present on the enamel-based coating.
• the glass article of the invention comprises at least one wax that is present in the enamel-based coating and on the enamel-based coating.
• the wax is present in the composition of the enamel-based coating.
• the wax can be distributed homogeneously in the composition of the coating.
• the wax may be distributed in a heterogeneous manner in the composition of said coating.
• the wax may be present in the thickness of the enamel-based coating but at a distance close to its surface (that in contact with the external environment).
• the composition of the enamel-based coating comprises between 0.1 to 20% by weight of wax. Too little wax will not achieve the desired effect. Too great a quantity of wax, beyond a certain value, brings nothing and even represents a disadvantage of an economic and ecological point in that this wax is subsequently burned during the heat treatment.
• the composition of the enamel-based coating comprises between 0.2 to 10% by weight of wax.
• the glass article is obtained according to a method comprising the following steps, in the order:
• the wax may be in the form of a fine powder, in the form of a more or less viscous liquid or in the form previously dispersed or solubilized in a liquid medium which may be composed water, one or more solvent (s), a polymeric matrix, one or more resins and / or a plasticizer, a wetting agent, etc.
• a liquid medium which may be composed water, one or more solvent (s), a polymeric matrix, one or more resins and / or a plasticizer, a wetting agent, etc.
• the wax in one of the above forms is added directly into the enamelled composition which is preferably in liquid form, more or less viscous.
• the resulting composition can then be mixed in a known manner.
• the enamelled composition comprising the wax on the glass sheet.
• the screen printing method can also be used, especially when only portions of the glass sheet are to be coated.
• the coating obtained is dried and / or crosslinked (if it comprises crosslinkable elements), for example by means of heat (in an oven, for example) and / or thanks to UV or IR radiation.
• This step allows the coating to harden and adhere to the glass sheet.
• the enamel is not yet melted or sintered.
• this step is preferably carried out at a temperature of at least 150 ° C and / or not exceeding 300 ° C; for 1 to 20 minutes in a static oven or for 5 to 10 minutes in an industrial oven.
• the temperature at the glass surface will not exceed 250 ° C.
• the wax is present on the enamel-based coating.
• wax present on the coating is meant that the wax is deposited on the coating but is not part of its composition.
• the wax is present on the enamel-based coating in the form of a film.
• the film may consist mainly of wax.
• the film may comprise at least 80% wax and even more preferably at least 90% wax.
• the wax film according to the invention may comprise minor constituents such as, for example, wetting agents or mineral fillers.
• the wax is in direct contact with the enamel-based coating.
• the film has a thickness that varies between 0.5 and 60 microns. Film thickness is also understood to mean the average geometrical thickness.
• the glass article is obtained according to a method comprising the following steps, in the order:
• the wax is deposited on the enamel-based coating by various known coating methods.
• the wax may be deposited on the coating by a spraying process.
• the wax in the form of a powder or a more or less viscous liquid is previously dispersed or solubilized in a liquid medium which may be composed of water, one or more solvent (s), a polymer matrix, d one or more resins and / or a plasticizer, a wetting agent, etc.
• an additional drying step may be required. Conventionally, it can be done by heating the glass sheet to a suitable temperature to cause evaporation of the solvent and / or water.
• the heat used for the previous step of drying / crosslinking the enamel-based coating can be used for this step.
• the glass article comprises at least one wax which is present in the coating and on the coating. This embodiment therefore combines the first two embodiments described above.
• the glass article is obtained according to a method comprising the following steps, in the order:
• the wax present in the coating is the same as the wax present on the coating.
• the wax present in the coating is different from the wax present on the coating.
• the article according to the invention may be heat treated, in particular it may be heat treated for quenching or also for bending.
• heat treatment is meant treatment at temperatures of not less than 500 ° C and preferably not less than 600 ° C.
• the drying and / or crosslinking step therefore does not constitute a "heat treatment” within the meaning of the invention.
• the enamel-based coating melts and sinter and the wax, exclusively of organic nature, is burned.
• the invention therefore covers an article which is not heat-treated but which can be heat-treated (referred to as "hardenable” or "bendable" article).
• Articles according to the invention may have various applications. These items can for example be used for decorative applications, single-sided or double-sided, such as furniture doors, partitions, wall coverings, shelves, tables, balustrades, etc. They can also be used for automotive applications such as windshields, for example if the enamel-based coating is applied to the periphery of the glass sheet.
• the enamel-based coating of the invention can be colored. If the article is heat-treated, the color may change during processing, depending on the composition of the coating. If this occurs, it is possible to take into account and adapt the enamelled composition so that the color of the glass article, after its heat treatment, is that desired.
• the following examples illustrate the invention, without intention to limit in any way its coverage.
• a 4 mm thick floated clear glass sheet was conveyed on a conveyor belt. It is first washed in a normal way. It then goes under a curtain applicator where it is coated with an enamelled composition.
• the enameled composition deposited on the glass sheet comprises:
• the resulting coating is then dried and crosslinked at a temperature of 185 ° C for 5 minutes.
• the thickness of the coating is approximately 50 microns.
• the coated glass sheet is then deposited on rubber type belts to allow its cutting and lapping. It is then washed in an industrial washing machine and then quenched in known manner (heating in an oven at 670 ° C for 3 minutes followed by rapid cooling to room temperature).
• a floated clear glass sheet was 4 mm thick was conveyed on a conveyor belt. It is first washed in a normal way. It then goes under a curtain applicator where it is coated with an enamelled composition.
• the enameled composition deposited on the glass sheet comprises:
• the resulting coating is then dried and crosslinked at a temperature of 185 ° C for 5 minutes.
• the thickness of the resulting coating is approximately 50 microns.
• the coated glass sheet is then deposited on rubber type belts to allow its cutting and lapping. It is then washed in an industrial washing machine and then quenched in known manner (heating in an oven at 670 ° C for 3 minutes followed by rapid cooling to room temperature).
• the glass sheet which has been in contact with the belts has traces but which are less visible than for the previous example because of the black color. These traces are attenuated after washing but do not do not disappear completely. They are always present also after quenching.
• Floating clear glass sheets 4 mm thick were conveyed on a conveyor belt. They are first washed in a normal way. They then go under a curtain applicator where they are coated with an enamelled composition.
• the enameled composition deposited on the glass sheets is either:
• composition 1 82% by weight of a white enamel of the company FENZI (TEMPVER bianco 3302-928A), 9% by weight of a
• composition 2 82% by weight of a black enamel from FENZI company (TEMPVER TEMPVER nero 3400- ⁇ 990 ⁇ ) and 9% by weight of a Clearcoat from FENZI company and 9% by weight of solvent (Exsol D40), to which wax has been added.
• a black enamel from FENZI company (TEMPVER TEMPVER nero 3400- ⁇ 990 ⁇ )
• Exsol D40 solvent
• the waxes used are Lancowax waxes supplied by the Lubrizol reference company lanco TF1778 (polytetrafluoroethylene) and lanco PP1350 (polypropylene). These waxes were incorporated in the enamel composition as such, that is to say in powder form, or else in dispersed form in a liquid medium.
• the dispersions that have been used are:
• Dispersion 1 32% by weight of wax dispersed in a mixture of polyester and melamine; and Dispersion 2: 20% by weight of wax dispersed in an aliphatic petroleum distillate obtained between 140-200 ° C (reference ED40).
• the resulting coating is then dried and crosslinked at a temperature of 185 ° C for 5 minutes.
• the thickness of the coating is then approximately 50 microns.
• coated glass sheets are then stored and stored in piles. During their cutting and lapping, they are deposited on rubber-type belts to allow their handling and transport. They are then washed in an industrial washing machine and then quenched in the same manner as the comparative examples.
• the table shows, for each of Examples 3 to 15, the quantity and the shape of the wax added to the enamelled composition (1 or 2), and the visual evaluation of the black marks after cutting and lapping, after washing in a washing machine. and after quenching.
• Figure 2 shows photographs of the article of Example 4 (a) after handling and transport on the belts, (b) after washing in the washing machine and (c) after quenching.
• a 4 mm thick floated clear glass sheet was conveyed on a conveyor belt. It is first washed in a normal way. It then goes under a curtain applicator where it is coated with an enamelled composition.
• the enameled composition deposited on the glass sheet comprises:
• the resulting coating is then dried and crosslinked at a temperature of 185 ° C for 5 minutes in an oven.
• the thickness of the coating is then approximately 50 microns.
• FIG. 3 shows photographs of Example 16 (a) after handling and transport on the belts and (b) after quenching. These pictures illu 1i i C p o s t on pc om i also Strent that belts create the appearance of unsightly marks on the white coating and that the traces have disappeared after quenching.
• 3/5 not very visible traces
• 2/5 visible traces
• 1/5 very visible traces
• 0/5 very visible traces and very intense colors (product unfit for sale).

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• Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Composite Materials (AREA)
• Inorganic Chemistry (AREA)
• Surface Treatment Of Glass (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)
• Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
• Securing Of Glass Panes Or The Like (AREA)
• Details Of Rigid Or Semi-Rigid Containers (AREA)

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• 2010
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